Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion |
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| Authors: | Ruyi Zou Pei‐Zhou Li Yong‐Fei Zeng Jia Liu Ruo Zhao Hui Duan Zhong Luo Jin‐Gui Wang Ruqiang Zou Yanli Zhao |
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| Affiliation: | 1. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore;2. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, Henan, China;3. Singapore Peking University Research Centre for a Sustainable Low‐Carbon Future, Singapore, Singapore;4. Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, Department of Materials Science and Engineering College of Engineering, Peking University, Beijing, China;5. School of Materials Science and Engineering, Nanyang Technological University, Singapore, Singapore |
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| Abstract: | A highly porous metal‐organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn2(COO)4) and tetrameric (Zn4(O)(CO2)6), is successfully assembled by the reaction of a tricarboxylate ligand with ZnII ion. Subsequently, single‐crystal‐to‐single‐crystal metal cation exchange using the constructed MOF is investigated, and the results show that CuII and CoII ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation‐exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that CuII and CoII exchanged samples exhibit comparable CO2 adsorption capability to the pristine ZnII‐based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO2 with epoxides into related carbonates demonstrate that ZnII‐based MOF affords the highest catalytic activity as compared with CuII and CoII exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs. |
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| Keywords: | crystal engineering gas adsorption heterogeneous catalysis metal exchange metal‐organic frameworks |
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